Arsenic (As) and mercury (Hg) are highly toxic and contamination of water by these toxic elements is a major problem in many countries. Drinking water contaminated with As(III) and Hg(II) is associated with number of diseases such as skin lesions, keratosis, lung cancer, bladder cancer, kidney and respiratory failure, damage in the gastrointestinal tract and nervous system, impairment of speech, hearing and working etc. Contamination of As(III) has been reported in various parts of the world. Mercury is one of the heavy metals, highly toxic and harmful to the environment and human health. World Health Organization (WHO) has set the guidelines value 10 ppb for As(III). On the other hand, the US environmental protection agency (EPA) has set the maximum contaminant level of mercury in drinking water at 2 ppb. Thus determination of trace level of As(III) and Hg(II) at the guideline value set by WHO is of particular importance.
Various methods including hydride generation atomic fluorescence spectrometry, inductively coupled plasma atomic emission spectrometry (ICPAES), inductively coupled plasma mass spectrometry (ICPMS), fluorescence spectrophotometry, atomic absorption spectrometry etc. have been used for the detection of As(III) and Hg(II). Although these methods are successful in detecting As(III) and Hg(II) at sub-picogram to sub-nanogram level, they require expensive instruments, laboratory set-up and high operating cost. In contrast, the electrochemical methods are highly sensitive and involve low cost equipments and laboratory set up. The stripping voltammetric methods provide an efficient and reliable way to detect arsenic and mercury at low concentration. Au coated diamond and glassy carbon (GC) electrode and Au micro wire electrode have been employed for the detection of As(III) and Hg(II). Nevertheless, the major problems associated with the available electrochemical methods are (i) the interference due to other metal ions like Cu(II) present in the natural water (ii) high detection potential and (iii) interference due to supporting electrolyte anions. The concentration of Cu(II) in natural/drinking water is relatively high and it greatly interferes the measurement of As(III) due to the formation of intermetallic compound such as Cu3As2. Because of the interference due to Cu(II) and other supporting electrolyte anions, simultaneous determination has not been achieved. Furthermore, although As(III) and Hg(II) has been detected individually by electrochemical methods, simultaneous detection without interference from other coexisting ions has not been achieved.
For the electrochemical detection of As(III) and Hg(II), various solid electrodes have been employed in the art. Recently, the nano-sized metal particle electrochemically deposited electrodes have been used for the electroanalysis of As(II). Dai et. al and Simm et. al (Anal. Chem. 2004, 76, 5924-5929, Anal Chem. 2004, 76, 5051-5055) have reported the detection of arsenite using various electrodes. Ivadine et. al (Anal. Chem. 2006, 78, 6291-6298) utilized iridium-implanted boron-doped diamond (BDD) electrode for the detection of As(III) in ppb level. Very recently, Song and Swain (Anal Chem. 2007, 79, 2412-2420) have used the Au-coated diamond thin film electrode for the voltammetric determination of As(III) and As(V). Hrapovic et. al (Anal Chem. 2007, 79, 500-507) very recently reported the reusable Pt nanoparticle modified BDD microelectrodes for the oxidative determination of As(III).
The Au nanoparticle modified electrodes are known to be highly sensitive in the electrochemical detection of As(III). The major problems associated with the available electrochemical methods are (i) the interference due to other metal ions like Cu(II) present in the natural water (ii) high detection potential and (iii) interference due to supporting electrolyte anions. Cu(II) forms intermetallic compound such as Cu3As2 with As(III) and the accurate measurement of As(III) has not been achieved due to this interference.
In the case of Hg (II), unmodified and chemically modified electrodes have been used for its detection. Microelectrode and microelectrode arrays iridium and Au have been used for the detection of Hg(II) (Anal. Chem 2006, 78, 6291). Au microwire electrode has been recently used for the detection of Hg(II) in seawater (Anal. Chem. 2006, 78, 5052-5060). The major concern with these electrodes is the lack of long term stability and it requires medium exchange or surface regeneration.
PCT/GB06/03957 discloses electrochemical methods and materials for the detection of arsenic. In one aspect, arsenic is detected using a working electrode comprising particulate platinum. In another aspect, arsenic is detected using an electrode comprising indium tin oxide and particulate gold. Also provided are methods for the production of electrodes which involve the electrodeposition of Au onto indium tin oxide. The inventors have used the glassy carbon and indium tin oxide (ITO) electrodes modified with Pt and Au nanoparticles for the detection of As(III). As(III) has been detected on the Pt nanoparticle modified electrode by its oxidation to As(VI) whereas the measurement has been made on the Au nanoparticle by the oxidation of electrodeposited As(0). The detection limit achieved is 2.1 and 5 ppb on Pt and Au nanoparticle modified electrodes, respectively. The interference due to Cu(II) on the Au nanoparticle modified electrode has not been evaluated.
U.S. Pat. No. 5,385,708 entitled “Determination of ultra low levels of mercury” teaches a highly specific and sensitive electrode for the determination of ultra-low levels of mercury and an analytical system based on such electrode. The electrode is a glassy carbon electrode spin-coated with a monolayer of a highly sensitive reagent for the detection of mercury. The analytical method based on the use of this type of electrode is a voltammetric method. Concentrations of the order of as low as about 2.10−12 Moles mercury can be detected and measured. The reagent is 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane for the detection of Hg (II). This measurement is based on the complexation of Hg(II) with the aforementioned complexing agent. The concentration of Hg(II) has been monitored from the stripping current. Because this method is based on the complexation, regeneration of the electrode surface is critically necessary for repeated use.
U.S. Pat. No. 5,391,270 entitled ‘Detection and measurement of heavy metals’ discloses an improved method for measuring the presence and amount of a variety of metals contained in a sample. In the first step, all of the various forms of each metal are converted to a soluble metallic complex which is capable of being electrochemically reduced. Voltammetry is then used to determine the stripping current or charge characteristic of each metallic complex. Finally, the concentration of each metal can be calculated by insertion of the stripping current or charge value into an equation which correlates peak current or charge values with metal concentration. The metals which can be detected and quantified by using this method are gold, silver, bismuth, cadmium, thallium, and mercury. The concentration of heavy metals is determined using the stripping method. This method is based on the complexation of the metal ions with iodide ion. The metal ions have been converted into complexes of soluble form, which are electrochemically analyzed. The interference due to other metal ions has not been addressed.
In view of the limitations of the prior art and the lack of a sensor that can simultaneously detect and determined inorganic contaminants such as Arsenic (III), Mercury (II) and Copper (II), the need exists in the industry for such a system.